CN115093693A - High-impact-resistance thermoplastic elastomer and preparation method thereof - Google Patents
High-impact-resistance thermoplastic elastomer and preparation method thereof Download PDFInfo
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Abstract
The application discloses a high impact resistance thermoplastic elastomer and a preparation method thereof, which takes a thermoplastic elastomer material as a raw material, adds different coupling agents and polyborosiloxane, and carries out banburying granulation to enable the thermoplastic elastomer material to be crosslinked with other materials, thereby improving the microstructure of the thermoplastic elastomer material, improving the porosity of the thermoplastic elastomer material, effectively absorbing and storing energy by abundant cellular structures when the thermoplastic elastomer material is impacted at a high speed, and slowly releasing the energy after an impact load is removed, thereby improving the impact resistance of the thermoplastic elastomer material.
Description
Technical Field
The application relates to the field of thermoplastic elastomer materials, relates to a modification and preparation method of a thermoplastic elastomer, and particularly relates to a high-impact-resistance thermoplastic elastomer and a preparation method thereof.
Background
The thermoplastic elastomer material has the characteristics of aging resistance, oil resistance, convenient processing and wide processing mode, but the existing elastomer material is easy to deform in a large scale when being impacted at high speed, and has poor absorption effect on impact energy, so that the permeation energy is high and the impact resistance is poor.
Disclosure of Invention
The preparation method provided by the application takes a thermoplastic elastomer material as a raw material, different coupling agents and polyborosiloxane are added, the thermoplastic elastomer material is crosslinked with other materials through banburying granulation, the microstructure of the thermoplastic elastomer material is improved, the porosity of the thermoplastic elastomer material is improved, rich cell structures can effectively absorb and store energy when high-speed impact is applied, and the energy can be slowly released after impact load is removed, so that the impact resistance of the thermoplastic elastomer material is improved.
In a first aspect, the present application provides a method for preparing a high impact thermoplastic elastomer, comprising the steps of:
step one, drying a thermoplastic elastomer material raw material to obtain a product 1;
step two, banburying the product 1, polyborosiloxane and a coupling agent to obtain a product 2;
and step three, granulating the product 2 to obtain the product.
In a possible implementation manner, the Thermoplastic Elastomer material in the step one is any one of Thermoplastic polyurethane Elastomer rubbers (TPU), Thermoplastic elastomers (TPE), and Thermoplastic Polyester elastomers (TPEE).
In a possible implementation, the hardness of the thermoplastic elastomer material raw material is preferably 60 to 95A.
In one possible implementation manner, the drying process in the step one is as follows:
the thermoplastic elastomer material is dried in a drying oven at 105-110 ℃ for 8-9 hours to obtain a product 1.
In one possible implementation, the weight ratio of product 1, polyborosiloxane and coupling agent in step two is from 100: 10: 1 to 100: 15: 3.
In one possible implementation, the coupling agent in step two is a silane coupling agent.
In one possible implementation, the silane coupling agent is any one of Si69, Si75, KH550, KH650, and KH 750.
In a possible implementation manner, the banburying process in the second step is as follows:
the product 1, polyborosiloxane and a coupling agent are banburying in an internal mixer for 10-15 minutes to obtain a product 2, wherein the banburying temperature is 160-180 ℃.
In one possible implementation, the granulation process in step three is:
and granulating the product 2 in a granulator to obtain the product, wherein the granulation temperature of the granulator is 165-180 ℃, and the rotation speed is 15-25 Hz.
The application provides a high impact resistance thermoplastic elastomer and a preparation method thereof, which have the following technical effects:
the thermoplastic elastomer material is taken as a raw material, different coupling agents and polyborosiloxane are added, and banburying granulation is carried out to enable the thermoplastic elastomer material to be crosslinked with other materials, so that the microscopic pore structure of the thermoplastic elastomer material is improved, the porosity of the thermoplastic elastomer material is improved, the abundant cell structure can effectively absorb and store energy when the thermoplastic elastomer material is impacted at a high speed, and the energy can be slowly released after the impact load is removed, thereby improving the impact resistance of the thermoplastic elastomer material.
In a second aspect, the present application provides a high impact resistance thermoplastic elastomer prepared by any one of the preparation methods mentioned in the first aspect.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing a high impact resistance thermoplastic elastomer according to an embodiment of the present disclosure;
fig. 2 is a schematic structural diagram of an impact head used in the present application to compare impact resistance of thermoplastic elastomers according to various embodiments.
Detailed Description
To make the objects, technical solutions and advantages of the present application clearer, the technical solutions of the present application will be described clearly and completely with reference to fig. 1-2 of the present application, and it is obvious that the described embodiments are some, but not all embodiments of the present application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The application provides a preparation method of a high-impact-resistance thermoplastic elastomer, the process route of which is shown in figure 1, and the preparation method comprises the following steps:
step one, drying a thermoplastic elastomer material raw material to obtain a product 1;
step two, banburying the product 1, polyborosiloxane and a coupling agent to obtain a product 2;
and step three, granulating the product 2 to obtain the product.
As an example, the Thermoplastic Elastomer material in step one is any one of Thermoplastic polyurethane Elastomer (TPU), Thermoplastic Elastomer (TPE) and Thermoplastic Polyester Elastomer (TPEE).
As an example of implementation, the hardness of the thermoplastic elastomer material raw material is preferably 60 to 95A.
As an example, the drying process in the first step is:
the thermoplastic elastomer material is dried in a drying oven at 105-110 ℃ for 8-9 hours to obtain a product 1.
As an example of implementation, the weight ratio of product 1, polyborosiloxane and coupling agent in step two is from 100: 10: 1 to 100: 15: 3.
As an example of the implementation, the coupling agent in the second step is a silane coupling agent.
As one practical example, the silane coupling agent is any one of Si69, Si75, KH550, KH650 and KH 750.
As an example of the implementation, the banburying process in the second step is:
the product 1, polyborosiloxane and a coupling agent are banburying in an internal mixer for 10-15 minutes to obtain a product 2, wherein the banburying temperature is 160-180 ℃.
As an example of implementation, the granulation process in step three is:
and granulating the product 2 in a granulator to obtain the product, wherein the granulating temperature of the granulator is 165-180 ℃, and the rotating speed is 15-25 Hz.
The method for improving the impact resistance of the thermoplastic elastomer has the following technical effects:
the thermoplastic elastomer material is taken as a raw material, different coupling agents and polyborosiloxane are added, and banburying granulation is carried out to crosslink the thermoplastic elastomer material with other materials, so that the microstructure of the thermoplastic elastomer material is improved, the porosity of the thermoplastic elastomer material is improved, rich cell structures can effectively absorb and store energy when the thermoplastic elastomer material is impacted at high speed, and the energy can be slowly released after impact load is removed, thereby improving the impact resistance of the thermoplastic elastomer material.
The following describes the implementation of the above embodiments in detail by using specific examples.
Example one
Step 1, weighing 100 parts of TPU with the hardness of 60A, putting the TPU into a drying oven at 105 ℃, and drying the TPU for 8 hours;
step 2, weighing 10 parts of polyborosiloxane and 1 part of Si69 coupling agent, adding the polyborosiloxane and 1 part of 60A TPU material weighed in the step 1 into an internal mixer, and internally mixing for 15 minutes at the temperature of 175 ℃;
and 3, putting the material obtained in the step 2 into a granulator, and granulating at the temperature of 170 ℃ and the main machine rotating speed of 17.5Hz to obtain a sample 1.
Example two
Step 1, weighing 100 parts of TPU with the hardness of 75A, putting the TPU into a drying oven at 105 ℃, and drying the TPU for 8 hours;
step 2, weighing 15 parts of polyborosiloxane and 3 parts of Si69 coupling agent, adding the polyborosiloxane and 3 parts of the Si69 coupling agent into an internal mixer together with 100 parts of the TPU material of 75A weighed in the step 1, and internally mixing for 14 minutes at the temperature of 178 ℃;
and 3, putting the material obtained in the step 2 into a granulator, and granulating at the temperature of 173 ℃ and the rotating speed of a main machine of 19.5Hz to obtain a sample 2.
EXAMPLE III
Step 1, weighing 100 parts of TPU with the hardness of 95A, putting the TPU into a drying oven at 105 ℃, and drying the TPU for 8 hours;
step 2, weighing 13 parts of polyborosiloxane and 2 parts of Si75 coupling agent, adding the polyborosiloxane and 2 parts of the Si75 coupling agent and 100 parts of the TPU material of 95A weighed in the step 1 into an internal mixer, and internally mixing for 16 minutes at the temperature of 180 ℃;
and 3, putting the material obtained in the step 2 into a granulator, and granulating at the temperature of 176 ℃ and the main machine rotating speed of 18.5Hz to obtain a sample 3.
Example four
Step 1, weighing 100 parts of TPU with the hardness of 75A, putting the TPU into a drying oven at 105 ℃, and drying the TPU for 8 hours;
step 2, weighing 13 parts of polyborosiloxane and 2 parts of Si75 coupling agent, adding the polyborosiloxane and 2 parts of the Si75 coupling agent into an internal mixer together with 100 parts of 75A TPU material weighed in the step 1, and internally mixing for 15 minutes at the temperature of 169 ℃;
and 3, putting the material obtained in the step 2 into a granulator, and granulating at the temperature of 175 ℃ and the main machine rotating speed of 22.5Hz to obtain a sample 4.
EXAMPLE five
Step 1, weighing 100 parts of TPE with the hardness of 75A, putting the TPE into a drying oven at 105 ℃, and drying the TPE for 8 hours;
step 2, weighing 10 parts of polyborosiloxane and 1 part of KH550 coupling agent, adding the polyborosiloxane and 1 part of 75A TPE material weighed in the step 1 into an internal mixer, and internally mixing for 15 minutes at the temperature of 180 ℃;
and 3, putting the material obtained in the step 2 into a granulator, and granulating at the temperature of 178 ℃ and the main machine rotating speed of 18.5Hz to obtain a sample 5.
EXAMPLE six
Step 1, weighing 100 parts of TPE with the hardness of 75A, putting the TPE into a drying oven at 105 ℃, and drying the TPE for 8 hours;
step 2, weighing 10 parts of polyborosiloxane and 1 part of KH550 coupling agent, adding the polyborosiloxane and 1 part of 75A TPE material weighed in the step 1 into an internal mixer, and internally mixing for 18 minutes at the temperature of 165 ℃;
and 3, putting the material obtained in the step 2 into a granulator, and granulating at the temperature of 169 ℃ and the main engine rotating speed of 20.5Hz to obtain a sample 6.
EXAMPLE seven
Step 1, weighing 100 parts of TPE with the hardness of 60A, putting the TPE into a drying oven at 105 ℃, and drying the TPE for 8 hours;
step 2, weighing 15 parts of polyborosiloxane and 3 parts of KH650 coupling agent, adding the polyborosiloxane and 3 parts of 60A TPE material weighed in the step 1 into an internal mixer, and internally mixing for 15 minutes at the temperature of 180 ℃;
and 3, putting the material obtained in the step 2 into a granulator, and granulating at the temperature of 175 ℃ and the main machine rotating speed of 23.0Hz to obtain a sample 7.
Example eight
Step 1, weighing 100 parts of TPE with the hardness of 95A, putting the TPE into a drying oven at 105 ℃, and drying the TPE for 8 hours;
step 2, weighing 15 parts of polyborosiloxane and 3 parts of KH650 coupling agent, adding the polyborosiloxane and 3 parts of 95A TPE material weighed in the step 1 into an internal mixer, and carrying out internal mixing for 18 minutes at the temperature of 165 ℃;
and 3, putting the material obtained in the step 2 into a granulator, and granulating at the temperature of 179 ℃ and the host rotation speed of 17.5Hz to obtain a sample 8.
Example nine
Step 1, weighing 100 parts of TPEE with the hardness of 60A, putting the TPEE into a drying oven at 105 ℃, and drying the TPEE for 8 hours;
step 2, weighing 10 parts of polyborosiloxane and 1 part of KH650 coupling agent, adding the polyborosiloxane and 1 part of 60A TPE material weighed in the step 1 into an internal mixer, and carrying out internal mixing for 15 minutes at the temperature of 180 ℃;
and 3, putting the material obtained in the step 2 into a granulator, and granulating at the temperature of 176 ℃ and the main machine rotating speed of 24.5Hz to obtain a sample 9.
Example ten
Step 1, weighing 100 parts of TPEE with the hardness of 75A, putting the TPEE into a drying oven at 105 ℃, and drying the TPEE for 8 hours;
step 2, weighing 15 parts of polyborosiloxane and 3 parts of KH650 coupling agent, adding the polyborosiloxane and 3 parts of KH650 coupling agent into an internal mixer together with 100 parts of 75A TPEE material weighed in the step 1, and internally mixing for 17 minutes at the temperature of 166 ℃;
and 3, putting the material obtained in the step 2 into a granulator, and granulating at the temperature of 175 ℃ and the main machine rotating speed of 20.5Hz to obtain the sample 10.
EXAMPLE eleven
Step 1, weighing 100 parts of TPEE with the hardness of 95A, putting the TPEE into a drying oven at 105 ℃, and drying the TPEE for 8 hours;
step 2, weighing 15 parts of polyborosiloxane and 2 parts of KH750 coupling agent, adding the polyborosiloxane and 2 parts of KH750 coupling agent together with 100 parts of 95A TPEE material weighed in the step 1 into an internal mixer, and internally mixing for 13 minutes at the temperature of 180 ℃;
and 3, putting the material obtained in the step 2 into a granulator, and granulating at the temperature of 165 ℃ and the main machine rotating speed of 19.0Hz to obtain a sample 11.
Example twelve
Step 1, weighing 100 parts of TPEE with the hardness of 85A, putting the TPEE into a drying oven at 105 ℃, and drying the TPEE for 8 hours;
step 2, weighing 13 parts of polyborosiloxane and 3 parts of Si69 coupling agent, adding the polyborosiloxane and 3 parts of 85A TPEE material weighed in the step 1 into an internal mixer, and internally mixing for 16 minutes at the temperature of 178 ℃;
and 3, putting the material obtained in the step 2 into a granulator, and granulating at the temperature of 175 ℃ and the main machine rotating speed of 19.5Hz to obtain a sample 12.
EXAMPLE thirteen
Step 1, weighing 100 parts of TPEE with the hardness of 75A, putting the TPEE into a drying oven at 105 ℃, and drying the TPEE for 8 hours;
step 2, weighing 10 parts of polyborosiloxane and 1 part of KH550 coupling agent, adding the polyborosiloxane and 1 part of 75A TPEE material weighed in the step 1 into an internal mixer, and internally mixing for 15 minutes at the temperature of 175 ℃;
and 3, putting the material obtained in the step 2 into a granulator, and granulating at the temperature of 175 ℃ and the main machine rotating speed of 17.5Hz to obtain a sample 13.
In summary, all sample components are summarized, and table 1 is a summary table of coupling agents and polyborosiloxanes for the samples, as shown in table 1:
TABLE 1
Comparative sample 1, comparative sample 2 and comparative sample 3 in table 1 were obtained as follows:
and banburying and granulating the TPU material with the hardness of 75A at the banburying temperature of 175 ℃ for 15 minutes, at the granulator barrel temperature of 165-180 ℃ and at the main engine rotation speed of 17.5 to obtain a comparative sample 1.
And (3) carrying out banburying granulation on the TPE material with the hardness of 75A, wherein the banburying temperature is 175 ℃, the banburying time is 15 minutes, the temperature of a granulator cylinder is 165-180 ℃, and the rotating speed of a main engine is 17.5, so as to obtain a comparative sample 2.
And (3) carrying out banburying granulation on the TPEE material with the hardness of 75A at the banburying temperature of 175 ℃, the banburying time of 15 minutes, the temperature of a granulator cylinder of 165-180 ℃ and the rotating speed of a main engine of 17.5 to obtain a comparative sample 3.
The technical effects of the embodiment are as follows:
the porosity of the examples and comparative examples was measured by the BET method, and the impact resistance of the material was also measured.
Impact resistance test referring to the test method of GB/T2812-:
the transmission force and the transmission energy are measured on the lower bracket by a sensor, the smaller the transmission force and the transmission energy is, the higher the energy absorbed when the impact is received is, the stronger the impact resistance is, table 2 is a sample impact resistance comparison table, and the results are shown in table 2:
TABLE 2
In combination with table 1, it can be found that:
comparing the comparative sample 1 with the samples 1, 2, 3 and 4, wherein TPU is used as a raw material, and the porosity of the comparative sample 1 is lower than that of the samples 1, 2, 3 and 4; the impact test pass energy and permeability of comparative sample 1 were higher than those of samples 1, 2, 3, and 4; comparative sample 1 has lower impact resistance than sample 1, sample 2, sample 3, and sample 4.
Comparing the sample 2 with the sample 5, the sample 6, the sample 7 and the sample 8, wherein TPE is used as a raw material, and the porosity of the sample 2 is lower than that of the sample 5, the sample 6, the sample 7 and the sample 8; the impact test pass energy and permeability of comparative sample 2 were higher than those of samples 5, 6, 7, 8; comparative sample 2 has lower impact resistance than sample 5, sample 6, sample 7, and sample 8.
Comparing the comparison sample 3 with the samples 9, 10, 11, 12 and 13, wherein TPEE is used as a raw material, and the porosity of the comparison sample 3 is lower than that of the samples 9, 10, 11, 12 and 13; the impact test pass energy and permeability of comparative sample 3 are higher than those of samples 9, 10, 11, 12, 13; comparative sample 2 has lower impact resistance than sample 9, sample 10, sample 11, sample 12, and sample 13.
The porosity of TPU, TPE and TPEE materials is improved by adding the coupling agent and the polyborosiloxane, and the permeability and the permeation energy of the materials added with the coupling agent and the polyborosiloxane are lower than those of the comparative example by comparing the permeability and the permeation energy, which shows that the impact resistance of the thermoplastic elastomer added with the coupling agent and the polyborosiloxane is superior to that of the conventional thermoplastic elastomer.
The application also provides a high-impact-resistance thermoplastic elastomer prepared by the preparation method provided by the embodiment.
The above description is only for the specific embodiments of the present application, but the scope of the present application is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present application, and shall be covered by the scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Claims (10)
1. A method for preparing a high impact thermoplastic elastomer, characterized in that it comprises:
step one, drying a thermoplastic elastomer material raw material to obtain a product 1;
secondly, banburying the product 1, polyborosiloxane and a coupling agent to obtain a product 2;
and step three, granulating the product 2 to obtain the product.
2. The method for preparing a thermoplastic elastomer with high impact resistance according to claim 1, wherein the thermoplastic elastomer material is any one of thermoplastic polyurethane elastomer rubber (TPU), thermoplastic elastomer (TPE) and thermoplastic polyester elastomer (TPEE).
3. The method for preparing a high impact resistance thermoplastic elastomer according to claim 2, wherein the hardness of the raw material of the thermoplastic elastomer material is 60 to 95A.
4. The method for preparing a high impact resistance thermoplastic elastomer according to claim 1, wherein the drying process in the first step is as follows:
and drying the thermoplastic elastomer material raw material in an oven at 105-110 ℃ for 8-9 hours to obtain the product 1.
5. A process for the preparation of a high impact thermoplastic elastomer, as claimed in claim 1, characterized in that the weight ratio of said product 1, said polyborosiloxane and said coupling agent in step two is comprised between 100: 10: 1 and 100: 15: 3.
6. The method for preparing a high impact thermoplastic elastomer according to claim 1, wherein the coupling agent in the second step is a silane coupling agent.
7. The method for preparing a high impact thermoplastic elastomer according to claim 6, wherein the silane coupling agent is any one of Si69, Si75, KH550, KH650 and KH 750.
8. The method for preparing a high impact thermoplastic elastomer according to claim 1, wherein the banburying process in the second step is:
and banburying the product 1, the polyborosiloxane and the coupling agent in an internal mixer for 10-15 minutes to obtain the product 2, wherein the banburying temperature is 160-180 ℃.
9. The method for preparing a high impact resistance thermoplastic elastomer according to claim 1, wherein the granulation process in the third step is as follows:
and granulating the product 2 in a granulator to obtain the product, wherein the granulating temperature of the granulator is 165-180 ℃, and the rotating speed is 15-25 Hz.
10. Thermoplastic elastomer with high impact resistance, characterized in that it is prepared by the process according to any one of claims 1 to 9.
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| CN116284948A (en) * | 2023-03-28 | 2023-06-23 | 西安理工大学 | Preparation method of modified EVA elastomer |
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| CN113527832A (en) * | 2021-07-15 | 2021-10-22 | 中国科学院长春应用化学研究所 | Impact-resistant protective material based on thermoplastic elastomer and preparation method thereof |
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| CN109161073A (en) * | 2018-06-29 | 2019-01-08 | 广东威立瑞科技有限公司 | A kind of ageing-resistant anti-ballistic materials and preparation method thereof and cable protection pipe obtained |
| CN112080811A (en) * | 2020-09-22 | 2020-12-15 | 西安匹克玄铠新材料有限公司 | Strain sensitive fiber and preparation method thereof |
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